CN102146512B - Hamartite smelting separation process - Google Patents
Hamartite smelting separation process Download PDFInfo
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- CN102146512B CN102146512B CN2010101092905A CN201010109290A CN102146512B CN 102146512 B CN102146512 B CN 102146512B CN 2010101092905 A CN2010101092905 A CN 2010101092905A CN 201010109290 A CN201010109290 A CN 201010109290A CN 102146512 B CN102146512 B CN 102146512B
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Abstract
The invention discloses a hamartite smelting separation process. First optimal slag or/and second optimal slag mainly containing cerium (IV), thorium (IV) and fluorine, obtained by oxidative roasted salt acid leaching of hamartite, is/are used as raw materials, and extraction and separation of rare earth are performed. The process comprises the following steps of: 1) leaching the first optimal slag by using sulfuric acid to obtain sulfuric acid-rare earth solution and filter residue; or leaching the second optimal slag obtained by alkali conversion-hydrochloric acid dissolution of the first optimal slag by using sulfuric acid to obtain sulfuric acid-rare earth solution and filter residue; or leaching the mixed slag of the first optimal slag and the second optimal slag by using sulfuric acid to obtain sulfuric acid-rare earth solution and filter residue; 2) performing extraction separation on the sulfuric acid-rare earth solution obtained in the step 1) to obtain a rare earth compound, fluorine washing liquor, a pure cerium product and a thorium product; and 3) synthesizing a fluoride product by using the fluorine-containing alkali wastewater obtained by alkali conversion in the step 1) and the fluorine washing liquor obtained by the extraction separation in the step 2). The process has the advantages that: the recovery rate of the rare earth is obviously improved, the fluorine and the thorium (IV) are effectively reclaimed in a product form, the high-purity cerium product is obtained, reclamation of the rare earth and associated resources is realized, and the additional values of the resources are improved; and the process flow is simple, the consumption of acid and alkali is low, the production cost is low, and the process is environmentally-friendly.
Description
Technical field
The present invention relates to a kind of hamartite and smelt the processing method of separating, specifically take the excellent slag that obtains after hamartite oxidizing roasting-dissolving with hydrochloric acid or/and two excellent slags are raw material, the extraction of carrying out rare earth, thorium (IV) separates, and the rare earth in hamartite, thorium (IV), fluorine all reclaim with the form of product.This invention belongs to the rare-earth wet method field of metallurgy.
Background technology
Hamartite is the second largest rare earth resources of China, at present industrially generally raw ore is carried out to gravity treatment, flotation or magnetic separation, obtain the rare earth ore concentrate that content of rare earth is 50%～70%, concentrate is through oxidizing roasting, the fluorine carbonated rare earth is decomposed into rare earth oxide or fluorine rare earth oxide, cerium is oxidized to tetravalence, adopt the Leaching in Hydrochloric Acid trivalent rare earth, cerium (IV), fluorine and thorium (IV) are stayed in slag, be called an excellent slag, one excellent slag is decomposed with alkali, the washing defluorination, rare earth changes into oxyhydroxide and uses the excellent molten trivalent rare earth of hydrochloric acid again, cerium, thorium (IV) is still stayed in slag, be called two excellent slags, then leach and obtain rich cerium with the hydrochloric acid reduction.There is the following aspects problem in this technique: 1) the cerium product purity is low, is 97%-98% (CeO
2/ TREO) added value is low; 2) thorium enters waste residue and enters environment, causes radiocontamination, causes the wasting of resources simultaneously; 3) wash away fluorine by massive laundering in technique, fluorine enters in alkali waste water and enters environment with the form of Sodium Fluoride, and water resources is caused to serious pollution, causes the fluorine wasting of resources simultaneously; For problems such as current course of processing resource utilization are low, seriously polluted, the green of being badly in need of the exploitation highly effective is smelted separating technology, solve the pollution problem of the three wastes to environment, to reduce energetically the comprehensive utilization ratio of unit consumption of product and raising resource simultaneously, produce from the beginning of production decontamination, realize efficient utilization and the cleaner production of resource.
Chinese patent ZL95103694.7 disclose a kind of from fluorine-containing rare earth sulfate solution the method for extraction separation of quadravalence cerium, this invention is by hamartite oxidizing roasting, uses extraction agent P after adopting dilute sulphuric acid that rare earth, thorium etc. are all leached
507extraction quadrivalent cerium and thorium, thus with other Rare Earth Separation.The organic phase of extraction makes pure cerium after the reducing solution back extraction of fluorine-containing stablizer, and the yield of cerium is more than 95%.But the recovery of the not mentioned thorium of this patent of invention and fluorine and move towards problem, and fluorine enters in the cerium strip liquor, affects the cerium product purity, in addition P
507loading capacity is lower, easily forms supersaturation emulsification.
Chinese patent CN1254034A disclose a kind of from hamartite oxidizing roasting-sulphuric leachate the technique of extracting and separating cerium, thorium, this technique be take fluorine-containing rare earth sulfuric acid solution as raw material, first use trihydrocarbyl phosphine oxygen compound extracting and separating cerium (IV), then use primary amine kind of extractants extracting and separating thorium, and with other rare earths separation, can make the thorium of the cerium more than 95% in leach liquor and 99% be recycled.This technique is that separating cerium (IV), thorium (IV) and trivalent rare earth adopt three kinds of organic extraction systems, and trihydrocarbyl phosphine oxygen compound extraction agent is expensive, fluorine and cerium extract simultaneously in addition and back extraction simultaneously, and in the cerium product obtained, containing partially fluorinated cerium, fluorine can not reclaim separately.
Above-mentioned processing method is when extracting and separating obtains rare-earth products, other non-rare earth fluorine, thorium etc. are not effectively reclaimed, only considered the recovery of fluorine, just take into account the extraction of thorium, all do not proposed a process program that solves thoroughly environmental pollution and the wasting of resources.
Chinese patent 200710098732.9 disclose a kind of from the rare earth sulfate solution of thoriated (IV), fluorine and high price cerium the processing method of extracting and separating cerium, thorium (IV), fluorine and few cerium trivalent rare earth.In this patent, be also with dilute sulphuric acid, trivalent rare earth and cerium (IV), fluorine, thorium (IV) all to be leached and to enter rare earth sulfate solution after hamartite oxidizing roasting, in extraction separation process, trivalent rare earth is all stayed in raffinate.But, in the raffinate obtained by this technique, sulfuric acid rare earth concentration is low, acidity is high, need to consume a large amount of alkali neutralizations, and to sulfuric acid rare earth is converted to re chloride carry out again the extracting and separating trivalent rare earth by precipitation or abstraction and type-reverting, the extraction equipment that this method needs and extraction agent investment are large, this technique washes that fluorine liquid fluorine concentration is low, aluminium content is high, acidity is high in addition, also needs to add a large amount of alkali and fluorine while preparing sodium aluminum fluoride, and technique overall operation cost is high.
Summary of the invention
The present invention is directed to the variety of problems of current existence, the existing excellent molten technique of oxidizing roasting-hydrochloric acid is improved to innovation.Hamartite, through oxidizing roasting-Leaching in Hydrochloric Acid, leaches most of trivalent rare earth and obtains few cerium re chloride, directly adopt P
507deng extraction agent, trivalent rare earth is carried out to extracting and separating.Cerium (IV), thorium (IV), fluorine are not stayed in slag by Leaching in Hydrochloric Acid, the excellent slag sulfuric acid leaching obtained, perhaps utilize an excellent slag to carry out sulfuric acid leaching through the excellent two excellent slags after molten of alkali conversion-hydrochloric acid, perhaps the mixing slag of an excellent slag and two excellent slags carries out sulfuric acid leaching, the main sulphuric acid soln containing cerium (IV), thorium (IV) and fluorine obtained, then carry out extracting and separating cerium, thorium (IV) and fluorine.The purpose of this technique is to provide a kind of cleaning manufacturing technique method from the comprehensive recovering rare earth of hamartite, thorium (IV), fluorine, with the excellent molten technique of existing oxidizing roasting-hydrochloric acid, compare, eliminated the pollution to environment of thoriated waste residue and fluorine-containing waste liquid from source, with the disclosed technique of patent 200710098732.9, compare, reduce acid and alkali consumption, reduce running cost, easily on existing technique, on basis, carry out the scale operation transformation.
The technical solution used in the present invention is:
The excellent slag that the hamartite of take obtains mainly containing cerium (IV), thorium (IV), fluorine through oxidizing roasting Leaching in Hydrochloric Acid technique is or/and two excellent slags are raw material, and the extraction of carrying out rare earth separates, and its technique comprises the following steps:
1) an excellent slag obtains rare earth sulfate solution and filter residue with sulfuric acid leaching; Perhaps utilize an excellent slag alkali conversion-dissolving with hydrochloric acid to obtain two excellent slag sulfuric acid leachings, obtain rare earth sulfate solution and filter residue; Or the mixing slag of an excellent slag and two excellent slags is carried out to sulfuric acid leaching obtain rare earth sulfate solution and filter residue.
2) rare earth sulfate solution step 1) obtained carries out extracting and separating, obtains rare earth compound, washes fluorine liquid, pure cerium product, thorium product.
3) step 1) alkali transforms fluorine-containing alkaline waste water and the step 2 obtain) extracting and separating obtain wash fluorine liquid for the synthesis of the fluorochemical product.
Step 1) described one excellent slag is or/and two excellent slags are used the solution washing of pH2-4 before sulfuric acid leaching, purpose is the chlorion washed away in slag, because the existence of chlorion has a strong impact on the leaching yield of slag middle-weight rare earths, therefore require the chlorion weight percent concentration in the rear slag of washing to be less than 0.1%
Step 1) the mixing slag of described one excellent slag and two excellent slags, its mixed weight ratio is 1: 20～20: 1
Above-mentioned steps 1) described one excellent slag is or/and two excellent slag sulfuric acid leachings sulfuric acid concentration used is 0.5-6mol/l, and liquid-solid weight ratio is 12: 1～2: 1, and extraction temperature is 10～100 ℃, and the leaching yield of rare earth can reach more than 90%.
Step 1) rare earth sulfate solution obtained directly adopts acidic phosphorus extractant to carry out extracting and separating after adding the fluorion complexing agent.
Described one excellent slag is the slag that hamartite obtains after oxidizing roasting-Leaching in Hydrochloric Acid, and in leaching process, trivalent rare earth enters leach liquor, and quadrivalent cerium, thorium, fluorine are stayed in slag, and the excellent slag middle rare earth content obtained is 30～75wt%, wherein CeO
2/ TREO:60%-85%, fluorine content is 3～10wt%, thorium dioxide content is 0.05～0.8wt%.
Step 1) two excellent slag rare earth oxide content 20-70wt%, wherein CeO described in
2/ TREO:80%-98%, fluorine content 0.5-5wt%, thorium dioxide content is 0.1-1.0wt%.
Step 1) rare earth sulfate solution obtained adopts acidic phosphorus extractant to carry out the extraction of 1-10 stage countercurrent, by cerium (IV), thorium (IV), fluorine extracts into organic phase, load organic phases adopts sulfuric acid to carry out the washing of 1-10 stage countercurrent, the trivalent rare earth be extracted in organic phase is washed to water, Tai-Ace S 150 and nitric acid mixing solutions or aluminum nitrate washing fluorine for load organic phases after washing, make the fluorine more than 95% in organic phase enter water for remanufacture fluorine chemical product, wash the cerium containing in the acidic solution reduction reextraction organic phase of reductive agent for organic phase after fluorine, the thorium be enriched in organic phase is used sulfuric acid again, nitric acid, hydrochloric acid or its mixing solutions back extraction, blank organic phase is through washing, returning to extraction section after clarification recycles.
Step 1) alkaline filtrate and the step 2 that in, obtain in the alkali conversion procedure) extracting and separating obtain wash the merging of fluorine liquid for the preparation of the sodium aluminum fluoride product.
By the advantage of the excellent slag technique of sulfuric acid leaching one, be: after the oxidizing roasting dissolving with hydrochloric acid, the dissolved few cerium re chloride that obtains high density of most of trivalent rare earth, directly use P
507carry out the extracting and separating trivalent rare earth, separation costs is low; Cerium (IV), fluorine, thorium (IV) are enriched in an excellent slag uses sulfuric acid leaching again, can all be dipped into them in sulphuric acid soln and carry out the extracting and separating recovery, and obtain high-purity cerium, thorium (IV), fluorine product, has eliminated the pollution of thorium fluorine to environment.By the advantage of the excellent slag technique of sulfuric acid leaching two, be: after the oxidizing roasting dissolving with hydrochloric acid, the dissolved few cerium re chloride that obtains high density of most of trivalent rare earth, directly use P
507carry out the extracting and separating trivalent rare earth, the excellent slag obtained is excellent molten with alkali conversion-hydrochloric acid, and the whole strippings of trivalent rare earth that make to remain in an excellent slag separate with cerium; The two excellent slags that obtain are used sulfuric acid leaching again, in two excellent slags, trivalent rare earth content still less, cerium (IV), thorium (IV) are still stayed further enrichment in two excellent slags, sulfuric acid leaching efficiency is high, in the alkali step of converting, the part fluorine is converted to Sodium Fluoride and is dissolved in waste lye, this alkali lye can obtain with follow-up sulfuric acid system extracting and separating cerium, thorium (IV), fluorine washes together with fluorine liquid coupling and prepares the fluorine chemical product, and relatively original technique also has larger superiority.
The excellent slag alkali of part one transforms the excellent slag mixing leaching that dissolving with hydrochloric acid obtains two excellent slags and part, the feed liquid that can obtain suitable fluorine, sodium ratio prepares the fluorine chemical products such as sodium aluminum fluoride for recovery, F/Al than the condition that approaches 6 left and right under, adjust the pH value in 5 left and right by adding soda acid, the precipitation yield that can guarantee fluorine is greater than 98%, thereby realizes the high efficiente callback of rare earth associated resources fluorine.
The excellent slag of sulfuric acid leaching one or two excellent slag techniques all have larger superiority than original technique, and whole technological advantage of the present invention is:
1) take the excellent slag that hamartite oxidizing roasting Leaching in Hydrochloric Acid obtains is raw material, carry out the excellent two excellent slags after molten of turn-hydrochloric acid of sulfuric acid leaching or alkali and carry out sulfuric acid leaching, can make the trivalent rare earth of the overwhelming majority in hamartite oxidizing roasting ore deposit first by Leaching in Hydrochloric Acid, and separate with cerium (IV), thorium (IV), fluorine, obtain high density trivalent rare earth chloride soln and directly proceed to ripe P
507-hydrochloric acid system carries out extracting and separating.
When 2) rare earth yield obviously improves, fluorine, thorium (IV) by efficient recovery, and obtain high-purity cerium product with product form, have realized the recovery of rare earth and associated resources and have improved the resource added value.
3) technical process is simple, and acid and alkali consumption is few, and production cost is low, the technique environmental protection.The noun explanation:
One excellent slag: for the first time with the slag obtained after the dissolving with hydrochloric acid trivalent rare earth;
Two excellent slags: for the second time with the slag obtained after the dissolving with hydrochloric acid trivalent rare earth;
Mix slag: the slag obtained after an excellent slag and two excellent slags mix by a certain percentage.
The accompanying drawing explanation
Fig. 1: the excellent slag recovering rare earth of sulfuric acid leaching one and thorium, fluorine technique
Fig. 2: the excellent slag recovering rare earth of sulfuric acid leaching two and thorium, fluorine technique
Fig. 3: sulfuric acid leaching mixing slag recovering rare earth and thorium, fluorine technique
Embodiment
Embodiment 1
Hamartite obtains 1 ton of an excellent slag through the oxidizing roasting Leaching in Hydrochloric Acid, and wherein REO content is 30wt%, CeO
2/ TREO is 60%, and the weight content of fluorine is 3.0wt%, ThO
2content is 0.1wt%.The sulphuric acid soln that is 2 with pH is washed, chloride ion content after washing in an excellent slag is 0.01%, then at room temperature, take liquid-solid ratio as 12: 1 (weight ratio) with the sulfuric acid of 0.5mol/L, one excellent slag is leached, leach 10 hours, the leaching yield of rare earth is 93%, the rare earth sulfate solution 14.4m obtained
3, its Rare-Earth Content is in REO 19.4g/L, wherein CeO
2/ TREO is 85%, F
-concentration is 1.9g/L, ThO
2for 0.03g/L.
Rare earth sulfate solution adopts P
507and P
204synergic reagent carries out carrying out 5 stage countercurrent extractions according to comparing 1.5: 1, cerium (IV), thorium (IV), fluorine are extracted into organic phase, trivalent rare earth is stayed water and is separated with cerium (IV), thorium (IV), fluorine, load organic phases after extraction adopts 0.5mol/L sulfuric acid to carry out 4 stage countercurrent washings according to being in a ratio of 6: 1, the trivalent rare earth be extracted in organic phase washes water, Tai-Ace S 150 and 1mol/L nitric acid mixing solutions washing fluorine for load organic phases after washing, be configured Tai-Ace S 150 according to F/Al=1.4 (mol ratio), obtain containing aluminium wash fluorine liquid, its volume is 5m
3, Al wherein
3+for 5.664g/L, fluorine is 5.58g/L.
The organic phase of washing after fluorine obtains 99.97% pure cerium product through the hydrogen peroxide of 6mol/L hydrochloric acid and 1mol/L according to comparing 15: 1 reduction reextraction ceriums, be enriched in thorium in organic phase and use the 3mol/L sulphuric acid soln to carry out 8 stage countercurrent back extractions according to 18: 1 to obtain pure thorium compound again, blank organic phase is returned to extraction section and is recycled after washing, clarification.
Under normal temperature, to 4.83m
3add the above-mentioned 5m obtained through aluminium washing fluorine in the 1mol/L Fluorinse
3wash fluorine liquid containing aluminium, stirred, add NaOH solution to regulate pH value be 5 left and right simultaneously, obtains sodium aluminum fluoride, fluorine in fluorine liquid and the recovery of aluminium are washed in realization.
Embodiment 2
Hamartite obtains 1 ton of an excellent slag through the oxidizing roasting Leaching in Hydrochloric Acid, and wherein REO content is 75wt%, CeO
2/ TREO is 85%, and fluorine content is 10wt%, ThO
2content is 0.8wt%, the sulphuric acid soln that is 4 with pH, washed, the chloride ion content after washing in an excellent slag is 0.1%, then under 80 degree, take liquid-solid ratio with the sulfuric acid of 4mol/L is leached an excellent slag as 5.5: 1 (weight ratio), leach 1 hour, filtration, water washing filter cake, the leaching yield of rare earth is 95%, the rare earth sulfate solution Rare-Earth Content obtained is in REO 108g/L, wherein CeO
2/ TREO is 80%, F
-concentration is 14.4g/L, ThO
2concentration is 1.15g/L.
The rare earth sulfate solution obtained adopts P
507and P
204synergic reagent carries out 10 stage countercurrent extractions according to comparing 8: 1, cerium (IV), thorium (IV), fluorine are extracted into organic phase, trivalent rare earth is stayed water and is separated with cerium (IV), thorium (IV), fluorine, load organic phases after extraction adopts 0.5mol/L sulfuric acid to carry out 10 stage countercurrent washings according to comparing 4: 1, the trivalent rare earth be extracted in organic phase washes water, Tai-Ace S 150 and 0.5mol/L sulfuric acid mixed solution washing fluorine for load organic phases after washing, according to F/Al=1.4 (mol ratio) configuration Tai-Ace S 150, the fluorine liquid of washing obtained containing aluminium amasss as 10m
3, wherein Al is 9.64g/L, fluorine is 9.5g/L.
Wash organic phase after fluorine carries out the reduction reextraction cerium and obtains 99.98% pure cerium product according to being in a ratio of through 1mol/L hydrogen peroxide and 5mol/L hydrochloric acid at 10: 1, the thorium (IV) be enriched in organic phase uses the 4mol/L sulphuric acid soln to obtain pure thorium compound according to back extraction in 12: 1 again, and blank organic phase is returned to extraction section and recycled after washing, clarification.
90 ℃ of left and right, by the 10m obtained containing aluminium
3wash in fluorine liquid and add 690 kilograms of Sodium Fluorides, stirred, add NaOH to regulate pH value be 5 left and right simultaneously, obtains sodium aluminum fluoride, and fluorine in fluorine liquid and the recovery of aluminium are washed in realization.
Embodiment 3
Hamartite obtains 1 ton of an excellent slag through the oxidizing roasting Leaching in Hydrochloric Acid, and wherein REO content is 40wt%, CeO
2/ TREO is 85%, and fluorine content is 4.5wt%, ThO
2content is 0.3wt%, the sulphuric acid soln that is 2 with pH, washed, the chloride ion content after washing in an excellent slag is 0.01%, then under 100 ℃, take liquid-solid ratio with the sulfuric acid of 6.0mol/L is leached an excellent slag as 2: 1 (weight ratio), leach 2 hours, filtration, water washing filter cake, the leaching yield of rare earth is 95%, the rare earth sulfate solution Rare-Earth Content obtained is in REO 158g/L, wherein CeO
2/ TREO is 85%, F
-concentration is 17.8g/L, ThO
2concentration is 1.19g/L.
Rare earth sulfate solution adopts P
507carry out 6 stage countercurrent extractions according to being in a ratio of 12: 1, cerium (IV), thorium (IV), fluorine and iron are extracted into organic phase, trivalent rare earth is stayed water and is separated with cerium (IV), thorium (IV), fluorine, load organic phases after extraction adopts 1mol/L sulfuric acid to carry out 5 stage countercurrent washings according to comparing 4: 1, and the trivalent rare earth be extracted in organic phase washes water.Tai-Ace S 150 and 1mol/L nitric acid mixing solutions washing fluorine for load organic phases after washing, according to F/Al=1.4 (mol ratio) configuration Tai-Ace S 150 mixed solution, obtain containing aluminium wash fluorine liquid, its volume is 5m
3, Al wherein
3+for 8.678g/L, fluorine is 8.55g/L.
Wash organic phase after fluorine carries out the reduction reextraction cerium and obtains 99.99% pure cerium product according to comparing through 2mol/L hydrogen peroxide and 6mol/L hydrochloric acid at 12: 1, the thorium be enriched in organic phase obtains pure thorium compound with the sulphuric acid soln back extraction again, and blank organic phase is returned to extraction section and recycled after washing, clarification.
85 ℃ of left and right, by the 5m obtained containing aluminium
3wash in fluorine liquid and add 310 kilograms of Sodium Fluorides, stirred, add NaOH to regulate pH value be 5 left and right simultaneously, obtains sodium aluminum fluoride, and fluorine in fluorine liquid and the recovery of aluminium are washed in realization.
Embodiment 4
Hamartite obtains 1 ton of an excellent slag through the oxidizing roasting Leaching in Hydrochloric Acid, and wherein REO content is 55wt%, CeO
2/ TREO is 85%, and fluorine content is 8wt%, ThO
2content is 0.5wt%, the sulphuric acid soln that is 3 with pH, washed, the chloride ion content after washing in an excellent slag is 0.02%, then under 90 ℃, take liquid-solid ratio with the sulfuric acid of 2.0mol/L is leached an excellent slag as 8: 1 (weight ratio), leach 3 hours, filtration, water washing filter cake, the leaching yield of rare earth is 98%, the rare earth sulfate solution Rare-Earth Content obtained is in REO 56.2g/L, wherein CeO
2/ TREO is 85%, F
-concentration is 8.2g/L, ThO
2content 0.51g/L.
Rare earth sulfate solution adopts P according to being in a ratio of 5: 1
507carry out 5 stage countercurrent extractions, cerium (IV), thorium (IV), fluorine and iron are extracted into organic phase, trivalent rare earth is stayed water and is separated with cerium (IV), thorium (IV), fluorine, load organic phases after extraction adopts 0.8mol/L sulfuric acid to carry out 5 stage countercurrent washings according to comparing 6: 1, and the trivalent rare earth be extracted in organic phase washes water.
Tai-Ace S 150 and 1mol/L nitric acid mixing solutions washing fluorine for load organic phases after washing, according to F/Al=1.4 (mol ratio) configuration Tai-Ace S 150 mixed solution, obtain containing aluminium wash fluorine liquid, its volume is for being 10m
3, Al wherein
3+for 7.958g/L, fluorine is 7.84g/L.
Wash organic phase after fluorine carries out reduction reextraction cerium reduction reextraction cerium and obtains 99.99% pure cerium product according to comparing through 2mol/L hydrogen peroxide and 6mol/L hydrochloric acid at 12: 1, the thorium be enriched in organic phase obtains pure thorium compound with the 3mol/L sulphuric acid soln according to comparing back extraction in 15: 1 again, and blank organic phase is returned to extraction section and recycled after washing, clarification.
60 ℃ of left and right, by the 10m obtained containing aluminium
3wash in fluorine liquid and add 0.8mol/L Fluorinse 16.96m
3, stirred, add NaOH solution to regulate pH value be 5 left and right simultaneously, obtains sodium aluminum fluoride, fluorine in fluorine liquid and the recovery of aluminium are washed in realization.
Embodiment 5
Hamartite obtains an excellent slag and a leach liquor through the oxidizing roasting Leaching in Hydrochloric Acid, through alkali, transforms and the leaching of hydrochloric acid secondary, and the trivalent rare earth solution obtained and hydrochloric acid leachate merging for the first time are for extracting and separating lanthanum, praseodymium, neodymium, sm-eu-gd; It is 70wt% that the hydrochloric acid secondary leaches REO content in the two excellent slags that obtain, CeO
2/ TREO is 80%, and fluorine content is 5wt%, ThO
2content is 0.8wt%, the sulphuric acid soln that is 3 with pH, washed, chloride ion content after washing in two excellent slags is 0.01%, and then under 80 ℃, (weight ratio) leached as 7: 1 to take liquid-solid ratio with the sulfuric acid of 2mol/L, leach 2.5 hours, filtration, water washing filter cake, the leaching yield of rare earth is 97%, the rare earth sulfate solution 8.4m obtained
3, wherein REO content is 80.8g/L, wherein CeO
2/ TREO is 97%, F
-concentration is 5.8g/L, ThO
2concentration is 0.92g/L.
Rare earth sulfate solution adopts P
507carry out 3 stage countercurrent extractions according to comparing 4: 1, cerium (IV), thorium (IV), fluorine are extracted into organic phase, the trace trivalent rare earth is stayed water and is separated with cerium (IV), thorium (IV), fluorine, the sulfuric acid that load organic phases after extraction adopts 2mol/L is according to carrying out 4 stage countercurrent washings at 4: 1, after being extracted into micro-trivalent rare earth in organic phase and washing water, return and dissolve two excellent slags.
Tai-Ace S 150 and 1mol/L nitric acid mixing solutions washing fluorine for load organic phases after washing, according to F/Al=1.4 (mol ratio) configuration Tai-Ace S 150 mixed solution, obtain containing aluminium wash fluorine liquid, its volume is 5m
3, Al wherein
3+for 9.85g/L, fluorine is 9.7g/L.
The organic phase of washing after fluorine obtains 99.99% pure cerium product according to the cerium in 8: 1 reduction reextraction organic phases with 2mol/L hydrogen peroxide and 6mol/L hydrochloric acid, the thorium be enriched in organic phase obtains pure thorium compound with the sulfuric acid of 4mol/L according to comparing back extraction in 10: 1 again, and blank organic phase is returned to extraction section and recycled after washing, clarification.
Under normal temperature, by the 5m obtained containing aluminium
3wash in fluorine liquid and need to add 352 kilograms of Sodium Fluorides, stirred, add NaOH solution to regulate pH value be 5 left and right simultaneously, obtains sodium aluminum fluoride, and fluorine in fluorine liquid and the recovery of aluminium are washed in realization.
Embodiment 6
Hamartite obtains an excellent slag through the oxidizing roasting Leaching in Hydrochloric Acid, through alkali, transform, make rare earth be converted into oxyhydroxide, then leach for the second time with hydrochloric acid, the trivalent rare earth solution obtained and hydrochloric acid leachate merging for the first time are for extracting and separating lanthanum, praseodymium, neodymium, sm-eu-gd; 1 ton of the two excellent slag obtained, wherein REO content is 20%, CeO
2/ TREO is 98%, and fluorine content is 0.5wt%, ThO
2content is 0.6wt%, the sulphuric acid soln that is 3 with pH, washed, the chloride ion content after washing in two excellent slags is 0.01%, then under 70 ℃, take liquid-solid ratio as 8: 1 (weight ratio) with the sulfuric acid of 0.7mol/L, two excellent slags are leached, leached 3 hours, filtration, water washing filter cake, the leaching yield of rare earth is 98%, the rare earth sulfate solution 9.6m obtained
3, wherein REO content is 20.4g/L, wherein CeO
2/ TREO is 98%, F
-concentration is 0.51g/L, ThO
2concentration is 0.61g/L.
Rare earth sulfate solution adopts the P of non-saponification
507extraction is according to being in a ratio of 1: 1 and separating trivalent rare earth, cerium, thorium (IV), containing the raffinate of trivalent rare earth through in and removal of impurities, filter after, adopt carbonate deposition to reclaim a small amount of trivalent rare earth.Cerium-carrying, thorium (IV) organic phase adopt the sulfuric acid of 1mol/L to carry out 4 stage countercurrent washings according to comparing 7: 1, and the micro-trivalent rare earth be extracted in organic phase is washed into water, and washing lotion is returned and dissolved two excellent slags.
Add the Tai-Ace S 150 configuration according to F/Al=1.4 (mol ratio) and wash the fluorion of fluorine liquid wash load in organic, the fluorine liquid of washing obtained containing aluminium amasss as 2m
3, Al wherein
3+for 2.485g/L, fluorine is 2.45g/L.
Washing defluorination load organic phases obtains 99.99% pure cerium product with 6mol/L hydrochloric acid according to comparing 10: 1 ceriums in the back extraction organic phase with the 2mol/L hydrogen peroxide again, the thorium (IV) be enriched in organic phase obtains pure thorium compound with the sulfuric acid of 6mol/L according to comparing back extraction in 15: 1 again, and blank organic phase is returned to extraction section and recycled after washing, clarification.
95 ℃ of left and right, to 1.71m
30.5mol/L the 2m that adds aluminium washing defluorination to obtain in Fluorinse
3wash fluorine liquid containing aluminium, stirred, add NaOH solution to regulate pH value be 5.5 simultaneously, obtains sodium aluminum fluoride, realizes washing fluorine in fluorine liquid and the recovery of aluminium.
Embodiment 7
Hamartite obtains 1 ton of one excellent slag through the oxidizing roasting Leaching in Hydrochloric Acid, and wherein REO content is 58wt%, CeO
2/ TREO is 75%, and fluorine content is 9.0wt%, ThO
2content is 0.4wt%, and wherein 910 kilogram of one excellent slag is to carry out at 6: 1 after alkali transforms filtering, washing with 20% liquid caustic soda according to liquid-solid ratio, obtains the alkaline waste water and the filter cake that contain fluorine, and the alkaline waste water volume is 6.55m
3, containing F
-concentration is 10.0g/L, and the alkali transformation efficiency that calculates fluorine is 80%, and filter cake is with filtering and obtain 591 kilograms of two excellent slags after the 6mol/L dissolving with hydrochloric acid, and wherein REO content is 66.9%, and fluorine content is 2.8%, ThO
2content is 0.6wt%.After other 90 kilogram of one excellent slag and 591 kilogram of two excellent slag are mixed, the sulphuric acid soln that is 2 with pH washing dechlorination is less than 0.1wt%, then under 95 ℃, take liquid-solid ratio with the sulfuric acid of 2mol/L is leached mixing slag as 6: 1 (weight ratio), filtration, water washing filter cake, the leaching yield of rare earth is 98%, and the rare earth sulfate solution volume obtained is 4.9m
3, wherein REO content is 89.5g/L, CeO
2/ TREO is 83%, F
-concentration is 4.89g/L, ThO
2concentration is 0.79g/L.
Rare earth sulfate solution adopts P
507carry out 4 stage countercurrent extractions, be in a ratio of 5: 1, cerium (IV), thorium (IV), fluorine are extracted into organic phase, the trace trivalent rare earth is stayed water and is separated with cerium (IV), thorium (IV), fluorine, load organic phases after extraction adopts the sulfuric acid of 1mol/L to carry out 4 stage countercurrent washings, be in a ratio of 6: 1, the micro-trivalent rare earth be extracted in organic phase washes water, washing lotion is returned and is dissolved two excellent slags, load organic phases after washing is washed fluorine (according to fluorine aluminum ratio 1.6 (mol ratio) with addition of the aluminium amount) with aluminum nitrate solution, obtains F
-concentration is 4.0g/L, Al
3+concentration be 3.55g/L wash fluorine liquid 6.0m
3.
Wash organic phase after fluorine with 2mol/L hydrogen peroxide and 6mol/L hydrochloric acid mixed solution according to being in a ratio of 10: 1 ceriums in the back extraction organic phase, obtain 99.99% pure cerium product through 8 stage countercurrent back extractions, be enriched in thorium in organic phase again with the sulfuric acid of 4mol/L according to being in a ratio of 12: 1,6 stage countercurrents carry out back extraction and obtain pure thorium compound, and blank organic phase is returned to extraction section and recycled after washing, clarification.
50 ℃ of left and right, by in this example wash fluorine liquid and alkali turns the liquid mix and blend, and with acid or alkali regulation system pH value of solution=5 left and right, wash fluorine liquid and alkali and turn liquid and enter in the sodium aluminum fluoride precipitation, after end of synthesis, the yield of fluorine is more than 99%, without adding aluminium salt, villiaumite or sodium salt again.
Embodiment 8
Hamartite obtains 1 ton of one excellent slag through the oxidizing roasting Leaching in Hydrochloric Acid, and wherein REO content is 40wt%, CeO
2/ TREO is 85%, and fluorine content is 5wt%, ThO
2content is 0.3wt%, an excellent slag with 30% liquid caustic soda by liquid-solid ratio carry out at 4: 1 after alkali transforms filtering, washing, obtain the alkaline waste water that contains fluorine, wherein alkali turns liquid and amasss as 5.56m
3, F
-concentration is 6.0g/L, and the alkali transformation efficiency that calculates fluorine is 66.7%.The filter cake obtained reclaims three rare earths with the 6mol/L dissolving with hydrochloric acid, and filtration obtains 720 kilograms of two excellent slags, and (composition is that REO content is 41.7wt%, and CeO2/TREO is 85%, and fluorine content is 2.3wt%, ThO
2content is 0.4wt%):, the sulphuric acid soln that is 2 with pH washing is except wt0.1%, then under 95 ℃, take liquid-solid ratio with the sulfuric acid of 2mol/L is leached mixing slag as 4: 1 (weight ratio), filtration, water washing filter cake, filtration, water washing filter cake, water washing filter cake, the leaching yield of rare earth is 98%, and the rare earth sulfate solution volume obtained is 3.46m
3, wherein REO content is 85.1g/L, CeO
2/ TREO is 83%, F
-concentration is 4.72g/L, ThO
2concentration is 0.84g/L
The sulfur acid earth solution adopts P
507carry out 3 stage countercurrent extractions, be in a ratio of 4: 1, cerium (IV), thorium (IV), fluorine are extracted into organic phase, the trace trivalent rare earth is stayed water and is separated with cerium (IV), thorium (IV), fluorine, load organic phases after extraction adopts the sulfuric acid of 2mol/L to carry out 4 stage countercurrent washings, be in a ratio of 4: 1, the micro-trivalent rare earth be extracted in organic phase washes water, washing lotion is returned and is dissolved two excellent slags, load organic phases after washing is washed defluorination (according to fluorine aluminum ratio 2 (mol ratio) with addition of the aluminium amount) with aluminum nitrate solution, then through P
507obtain washing fluorine liquid 2.92m after extraction aluminium eccysis fluorine
3, F
-concentration is 5.70g/L, Al
3+concentration is 4.05g/L.
Wash 1mol/L hydrogen peroxide and 6mol/L hydrochloric acid mixed solution for organic phase after fluorine, obtain 99.99% pure cerium product according to being in a ratio of 10: 1 ceriums in the back extraction organic phase, the thorium be enriched in organic phase obtains pure thorium compound with the sulfuric acid of 3mol/L according to being in a ratio of back extraction in 15: 1 again, and blank organic phase is returned to extraction section and recycled after washing, clarification.
Fluorine liquid will all be washed 65 ℃ of left and right and alkali turns the liquid mix and blend, with acid or alkali regulator solution pH=6, wash fluorine liquid and alkali and turn liquid and generate sodium aluminum fluoride precipitation fully, after filtration, from waste water, calculate, in the sodium aluminum fluoride precipitation process, the yield of fluorine is greater than more than 99.5%, without the compound that adds fluorine or aluminium.
Embodiment 9
Hamartite obtains 1 ton of one excellent slag through the oxidizing roasting Leaching in Hydrochloric Acid: REO content is 30wt%, CeO
2/ TREO is 85%, and fluorine content is 3.0wt%, ThO
2content is 0.1wt%.Wherein 670 kilograms one excellent slag transforms by 3: 1 alkali of liquid-solid ratio with 30% liquid caustic soda, filters, washs, and obtains the alkaline waste water that contains fluorine, and wherein volume is 3.618m
3, containing F
-concentration is 5g/L, and the alkali that calculates fluorine is converted into 90%.The filter cake obtained is with filtering and obtain 469 kilograms of two excellent slags after the 6mol/L dissolving with hydrochloric acid, and wherein REO content is 32.1%, CeO
2/ TREO is 96%, and fluorine content is 0.4wt%, ThO
2content is 0.1wt%, after other 330 kilogram of one excellent slag and 469 kilogram of two excellent slag are mixed, the sulphuric acid soln that is 2 with pH washing is except wt0.01%, then under 95 ℃, take liquid-solid ratio with the sulfuric acid of 2mol/L is leached mixing slag as 5: 1 (weight ratio), filtration, water washing filter cake, the leaching yield of rare earth is 95%, the rare earth sulfate solution volume obtained is 4.79m
3, wherein REO content is 49.49g/L, CeO
2/ TREO is 83%, F
-concentration is 2.36g/L, ThO
2concentration is 0.10g/L.
Rare earth sulfate solution adopts P
507and P
204synergic reagent carries out 10 stage countercurrent extractions, be in a ratio of 2: 1, cerium (IV), pin (IV), fluorine are extracted into organic phase, trivalent rare earth is stayed water and is separated with cerium (IV), thorium (IV), fluorine, load organic phases after extraction adopts 0.5mol/L sulfuric acid to carry out 10 stage countercurrent washings, be in a ratio of 1: 1, the trivalent rare earth be extracted in organic phase washes water, the aluminum nitrate solution washing fluorine (being that 2.3 (mol ratios) are with addition of the aluminium amount according to the fluorine aluminum ratio) that load organic phases after washing is 0.5N by acidity, obtain F
-concentration is 3.77g/L, Al
3+concentration be 2.33g/L wash fluorine liquid 3m
3;
Wash organic phase after fluorine with containing 1mol/L hydrogen peroxide and 6mol/L hydrochloric acid mixed solution, according to comparing 10: 1, obtain 99.97% pure cerium product through the cerium in 8 stage countercurrent back extraction organic phases, thorium in organic phase again with the sulfuric acid of 3mol/L according to being in a ratio of 10: 1, obtain pure thorium compound through 5 stage countercurrent back extractions, blank organic phase is returned to extraction section and is recycled after washing, clarification.
Under normal temperature, all wash fluorine liquid and alkali turns the liquid mix and blend by what obtain above, and with about acid or alkali regulator solution pH=5, aluminium wherein and fluorion can generate sodium aluminum fluoride fully, in precipitation process, the rate of recovery of fluorine is greater than 99%, without the compound of introducing again aluminium or fluorine, can realize taking full advantage of fluorine.
Embodiment 10
Hamartite obtains 1 ton of one excellent slag through the oxidizing roasting Leaching in Hydrochloric Acid, and wherein REO content is 75wt%, CeO
2/ TREO is 90%, and fluorine content is 10wt%, ThO
2content is 0.8wt%.Wherein 80% one excellent slag filters, washs after transforming with sodium hydroxide, obtains the alkaline waste water that contains fluorine, and wherein volume is 7.6m
3, containing F
-concentration is 10g/L, and what calculate fluorine is converted into 95%.The filter cake obtained is with filtering and obtain 680 kilograms of two excellent slags after dissolving with hydrochloric acid, and wherein REO content is 32.1%, CeO
2/ TREO is 68.8%, and fluorine content is 0.6wt%, ThO
2content is 0.9wt%, by after other 20% 1 excellent slag and whole two excellent slags mixing, the sulphuric acid soln that is 2 with pH washing dechlorination is less than 0.1wt%, then under 95 ℃, take liquid-solid ratio with the sulfuric acid of 2mol/L and leached mixing slag as 12: 1 (weight ratio), filter the water washing filter cake, the leaching yield of rare earth is 95%, and the rare earth sulfate solution volume obtained is 12.67m
3, middle REO content is 46.33g/L, CeO
2/ TREO is 93%, F
-concentration is 1.78g/L, ThO
2concentration is 0.59g/L.
Rare earth sulfate solution adopts P
507and P
204synergic reagent carries out 6 stage countercurrent extractions, according to being in a ratio of 2: 1, cerium (IV), thorium (IV), fluorine are extracted into organic phase, trivalent rare earth is stayed water and is separated with cerium (IV), thorium (IV), fluorine, load organic phases after extraction adopts 1mol/L sulfuric acid, according to being in a ratio of 1: 1, carry out 6 stage countercurrent washings, the trivalent rare earth be extracted in organic phase washes water, the aluminum nitrate solution washing defluorination (being that 1.4 (mol ratios) are with addition of the aluminium amount according to the fluorine aluminum ratio) that load organic phases after washing is 0.2mol/L by acidity, obtain washing fluorine liquid 4m
3, F wherein
-concentration is 5.7g/L, Al
3+concentration is 5.58g/L.
Wash the cerium in organic phase after fluorine and obtain 99.99% pure cerium product according to comparing 10: 1,6 stage countercurrent back extractions with 1mol/L hydrogen peroxide and 6mol/L hydrochloric acid, be enriched in thorium in organic phase again with the sulfuric acid of 3mol/L according to being in a ratio of 4: 1,5 stage countercurrent back extractions obtain pure thorium compound, and blank organic phase is returned to extraction section and recycled after washing, clarification.
At 95 ℃, fluorine liquid will all be washed and alkali turns the liquid mix and blend, and with acid or alkali regulator solution pH=5.5, synthetic cryolite, aluminium wherein and fluorion can generate sodium aluminum fluoride fully, in precipitation process, the rate of recovery of fluorine is greater than 99%, without the compound of introducing again aluminium or fluorine, can directly realize taking full advantage of fluorine.
Claims (8)
1. a hamartite smelting separation process, it is characterized in that, the excellent slag obtained after oxidizing roasting Leaching in Hydrochloric Acid trivalent rare earth with hamartite, obtain two excellent slags through alkali conversion-dissolving with hydrochloric acid again, the mixing slag of two excellent slags or an excellent slag and two excellent slags of take is raw material, the extraction of carrying out cerium, thorium, fluorine separates, and its technique comprises the following steps:
1) the mixing slag of two excellent slags or an excellent slag and two excellent slags is less than 0.1% with the solution washing of pH2-4 to chlorion weight percent concentration wherein, then uses sulfuric acid leaching, obtains rare earth sulfate solution and filter residue;
2) rare earth sulfate solution step 1) obtained carries out extracting and separating, and to load organic phases, adopts Tai-Ace S 150 and nitric acid mixing solutions or aluminum nitrate to wash fluorine again, obtains rare earth compound, washes fluorine liquid, pure cerium product, thorium product;
3) alkali is transformed to fluorine-containing alkaline waste water and the step 2 obtain) extracting and separating obtain wash fluorine liquid for the synthesis of the fluorochemical product.
2. hamartite smelting separation process according to claim 1, it is characterized in that, described one excellent slag is the slag that hamartite obtains after oxidizing roasting-Leaching in Hydrochloric Acid, in leaching process, trivalent rare earth enters leach liquor, quadrivalent cerium, thorium, fluorine are stayed in slag, the excellent slag middle rare earth content obtained is 30～75wt%, wherein CeO
2/ TREO:60%-85%, fluorine content 3～10wt%, thorium dioxide content is 0.05～0.8wt%.
3. hamartite smelting separation process according to claim 1, is characterized in that step 1) described in two excellent slag middle rare earth content 20～70wt%, wherein CeO
2/ TREO:80%-98%, fluorine content 0.5-5wt%, thorium dioxide content is 0.1～1.0wt%.
4. hamartite smelting separation process according to claim 1, it is characterized in that, step 1) the mixing slag sulfuric acid leaching sulfuric acid concentration used of described two excellent slags or an excellent slag and two excellent slags is 0.5-6mol/l, and liquid-solid weight ratio is 12: 1～2: 1, and extraction temperature is 10～100 ℃.
5. hamartite smelting separation process according to claim 1, is characterized in that, described step 3) in synthetic fluorochemical product be the sodium aluminum fluoride product.
6. hamartite smelting separation process according to claim 1, is characterized in that step 1) in the excellent slag mentioned and the mixing slag of two excellent slags, wherein their weight ratio is 1: 20～20: 1.
7. hamartite smelting separation process according to claim 1, is characterized in that step 1) rare earth sulfate solution that obtains of two excellent slag sulfuric acid leachings directly adopts acidic phosphorus extractant to carry out extracting and separating after adding the fluorion complexing agent.
8. hamartite smelting separation process according to claim 1, it is characterized in that, step 2) extracting and separating of described rare earth sulfate solution, adopt acidic phosphorus extractant to carry out the extraction of 2-10 stage countercurrent, by quadrivalent cerium, thorium, fluorine extracts into organic phase, load organic phases adopts sulfuric acid to carry out the washing of 2-10 stage countercurrent, the trivalent rare earth be extracted in organic phase is washed to water, Tai-Ace S 150 and nitric acid mixing solutions or aluminum nitrate washing fluorine for load organic phases after washing, make the fluorine more than 95% in organic phase enter water for remanufacture fluorine chemical product, wash the cerium containing in the acidic solution reduction reextraction organic phase of reductive agent for organic phase after fluorine, the thorium be enriched in organic phase is used sulfuric acid again, nitric acid, hydrochloric acid or its mixing solutions back extraction, empty organic phase is returned to extraction section and is recycled after the washing clarification.
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